CN108232171A - A kind of high load sulphur lithium sulfur battery anode material and its preparation method and application - Google Patents
A kind of high load sulphur lithium sulfur battery anode material and its preparation method and application Download PDFInfo
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- CN108232171A CN108232171A CN201810075461.3A CN201810075461A CN108232171A CN 108232171 A CN108232171 A CN 108232171A CN 201810075461 A CN201810075461 A CN 201810075461A CN 108232171 A CN108232171 A CN 108232171A
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Abstract
The invention discloses a kind of high load sulphur lithium sulfur battery anode materials and its preparation method and application, and the preparation method that height carries sulphur lithium sulfur battery anode material is by C containing g3N4, graphene oxide, sodium thiosulfate and inorganic acid dispersion liquid carry out hydro-thermal reaction to get sulphur/graphene composite material that sulfur content can reach 60~88% is carried；This method is easy to operate, at low cost, is conducive to industrialized production, and be used to prepare lithium-sulfur cell using composite material as lithium sulfur battery anode material, shows good cyclical stability and high specific discharge capacity.
Description
Technical field
The present invention relates to a kind of lithium sulfur battery anode material, more particularly to a kind of high load sulphur lithium sulfur battery anode material, with
And using g-C3N4The high method for carrying sulphur lithium sulfur battery anode material is synthesized as template, further relates to lithium sulfur battery anode material
Application in the lithium-sulfur cell for preparing electrochemical performance, belongs to lithium-sulfur cell technical field.
Background technology
The active material of lithium sulfur battery anode material is sulphur, and cathode is lithium metal.Elemental sulfur is as lithium-sulphur cell positive electrode material
The theoretical specific capacity of material is up to 1675mA h g-1, theoretical energy density 2600Wkg-1, while the price of elemental sulfur is low, safety
It is nontoxic, nature rich content, therefore lithium-sulfur cell is received and is greatly paid close attention to.However, lithium-sulfur cell system also exists at present
Some serious problems：(1) elemental sulfur and its discharging product Li2S、Li2S2It is electronic body；(2) intermediate product vulcanizes more
Lithium is soluble in electrolyte, and shuttles between positive electrode and negative electrode, and the loss and coulombic efficiency for causing active material reduce；(3) it fills
In discharge process, mutually converting between sulphur and lithium sulfide causes volume expansion and contraction, leads to electrode material structural damage
Deng.Research shows that graphene has larger specific surface area and higher electric conductivity, the electrochemistry of active sulfur can be effectively improved
Performance.But C-C keys are nonpolar bonds in graphene sheet layer, with sulphur interact it is weaker, and with sulphur compound tense, graphene sheet layer
Between stack serious, it is relatively low to carry sulfur content.Therefore it is a technical problem to be solved urgently that it is low, which to carry sulfur content, for graphene.
Invention content
There is the problem of load sulfur content is low during preparing lithium sulphur positive electrode for graphene in the prior art, leading to stone
Application of the black alkene in high-performance lithium-sulfur cell is limited to, and of the invention first purpose is to be to provide a kind of load sulfur content height
Up to 60~88%, and carry the good lithium-sulfur cell graphene/sulfur composite positive electrode material of sulphur stability.
Another object of the present invention is to be that providing a kind of height for preparing easy to operate, at low cost carries sulphur lithium sulphur electricity
The method of pond positive electrode, this method is with g-C3N4For template, capture sulphur using it and it is made largely to be supported on graphene oxide
On lamella, high load sulfur content graphene/sulfur composite positive electrode material is obtained.
Third object of the present invention is to be to provide the high application for carrying sulphur lithium sulfur battery anode material, is prepared with it
Lithium-sulfur cell show good cyclical stability and high specific discharge capacity.
In order to realize above-mentioned technical purpose, the present invention provides a kind of high preparation sides for carrying sulphur lithium sulfur battery anode material
Method, this method is will be containing g-C3N4, graphene oxide, sodium thiosulfate and inorganic acid dispersion liquid carry out hydro-thermal reaction to get.
Preferred scheme, graphene oxide and g-C3N4Mass ratio be 10:5~20.
More preferably scheme, the g-C3N4By dicyanodiamine and/or melamine in protective atmosphere or air atmosphere, with
And it calcines and obtains under 400~600 DEG C of temperature conditions.That obtained by this method is the g-C with lamellar structure3N4。
More preferably scheme, the graphene oxide are made by improved Hummers methods.It is prepared by improved Hummers methods
Graphene oxide is the method for preparing graphene oxide relatively common in the prior art.It is prepared by improved Hummers methods
Graphene oxide have that degree of oxidation is high, and with two-dimensional sheet structure.Typical improved Hummers methods prepare oxidation stone
Black alkene, such as：The concentrated sulfuric acid of 23mL 98% is added in round-bottomed flask, under ice bath and stirring condition, is slowly added to 0.5g nitric acid
Sodium after sodium nitrate is completely dissolved, adds in the expanded graphite powder of 1g；After 20min, it is slowly added to 3g potassium permanganate in batches, controls
Temperature processed is below 5 DEG C.After 30min, round-bottomed flask is transferred in oil bath pan, continues to stir 2h under the conditions of 35 DEG C；Control temperature
Degree adds in 46mL deionized waters into flask at 98 DEG C, continues to stir 30min；Then the 3%H of 30mL is added in thereto2O2；With
5% hydrochloric acid and deionized water centrifuge washing is repeatedly to neutral；Dialysis treatment in bag filter is placed it in again；Dialysis treatment it
Afterwards, its concentration is measured, is placed in refrigerator and is protected from light refrigeration.
The mass ratio of more preferably scheme, graphene oxide and elemental sulfur is 8~12:5；Wherein, the quality of elemental sulfur with
With inorganic acid the elemental sulfur quality of disproportionated reaction generation occurs for sodium thiosulfate to calculate.The present invention is using sodium thiosulfate in acid
Property under the conditions of the elemental sulfur of disproportionated reaction generation Nano grade occurs, load in situ is carried out to graphene.Inorganic acid can be salt
Acid or sulfuric acid etc..Such as Na2S2O3+ 2HCl=2NaCl+SO2↑+S↓+H2O.The mass ratio of graphene oxide and elemental sulfur is
8~12:When 5, in the sulphur and graphene oxide composite material of generation, sulfur content is carried about in the range of 60~88%；Graphite oxide
The mass ratio of alkene and elemental sulfur is 8~10:When 5, in the sulphur and graphene oxide composite material of generation, sulfur content is carried 74~88%
In the range of.Sulfur content is carried in the composite material of the present invention can arbitrarily regulate and control in the range of 60~88%.
More preferably scheme, the hydrothermal reaction condition are：At a temperature of 140~200 DEG C, react 8~16 hours.
The present invention also provides a kind of high load sulphur lithium sulfur battery anode materials, are prepared by the above method.
The present invention also provides a kind of high applications for carrying sulphur lithium sulfur battery anode material, are applied to lithium-sulfur cell.
Technical scheme of the present invention key is in sulphur and graphene oxide recombination process using class graphitic nitralloy carbon (g-
C3N4) as template.g-C3N4Molecular structure in triazine ring or 3s- triazine rings one tool is connected to form by end N atoms
There are the planar network structure of the infinite expanding of similar graphite, therefore, g-C3N4There is two dimension between lamella and graphene oxide layer
Long-range acts on.Meanwhile g-C3N4C-N keys in molecular structure are polar bonds, and the chemical bond power between sulphur chain is stronger, can
To adsorb elemental sulfur；Meanwhile it is experimentally confirmed, g-C3N4It can be using partial hydrolysis to be readily soluble under the hydrothermal condition of high temperature and pressure
In the cyanuric acid small molecule of hot water, it can capture sulphur using these polar micromolecules and it is made largely to be supported on graphene film
On layer.Therefore, g-C3N4Comprising triazine ring and sulphur and graphene oxide have dual strong interaction, can indirectly will be largely
Sulphur is stable, equably compound with graphene oxide, substantially increases the load sulfur content and load stability of graphene oxide.
The high preparation method for carrying sulphur lithium sulfur battery anode material of the present invention includes step in detail below：
1) using dicyanodiamine and/or melamine as raw material, 3~5h of calcining is carried out at 400~600 DEG C, product is filled
Divide grinding, obtain the g-C with laminated structure3N4；
2) graphene oxide is prepared using improved Hummers methods；
3) by g-C3N4With sodium thiosulfate ultrasonic disperse, graphene oxide dispersion, further ultrasonic disperse are added
Afterwards, hydrochloric acid is added in, mixed dispersion liquid is transferred in hydrothermal reaction kettle, and it is small that hydro-thermal reaction 8~16 is carried out at a temperature of 140~200 DEG C
When, product is filtered, wash, is dried, obtains graphene/sulphur anode composite material.
The high sulphur lithium sulfur battery anode material that carries of the present invention is used to prepare lithium-sulphur cell positive electrode：Height is being carried into sulphur lithium-sulfur cell just
Pole material and acetylene black, polytetrafluoroethylene (PTFE) in mass ratio 6:2:2 mixing by drying, cut out film, and tabletting obtains positive plate.
Compared with the prior art, the advantageous effects that technical scheme of the present invention is brought：
1) the high sulphur lithium sulfur battery anode material that carries of the invention is prepared that carry sulphur stability good, and carries sulfur content and be up to 88%
The compound lithium sulfur battery anode material of graphene/sulphur.
2) the high sulphur lithium sulfur battery anode material that carries of the invention is for lithium-sulfur cell, in 0.2C (335mA g-1) under conditions of
Charge-discharge test is carried out, first week discharge capacity is up to 1041.2mA h g-1, and after 100 circle of cycle, specific discharge capacity is still
So it is maintained at 480mAh g-1, and under conditions of high magnification (0.5C and 1C), cycle efficieny can be stablized more than 96% always.
3) the high preparation method for carrying sulphur lithium sulfur battery anode material of the invention is simple, strong operability, cost of material are low, and
Environmental sound is conducive to industrialized production.
4) high carry of the invention utilizes g-C for the first time in sulphur lithium sulfur battery anode material preparation process3N4As template, energy
It enough greatly improves the load sulfur content of graphene oxide and carries sulphur stability, obtain graphene/sulphur complex lithium sulphur of high electrochemical performance
Cell positive material.
5) high carry of the invention utilizes g-C in sulphur lithium sulfur battery anode material preparation process3N4It can pass through as template
g-C3N4Dosage realize to carry sulfur content Effective Regulation.
Description of the drawings
【Fig. 1】XRD diagram for elemental sulfur and graphene/sulfur compound (GS)；
【Fig. 2】Thermogravimetric curve for graphene in elemental sulfur and embodiment 1/sulfur compound graphene/sulfur compound (GS)；
【Fig. 3】Thermogravimetric curve for graphene/sulfur compound in embodiment 2；
【Fig. 4】For g-C3N4(a) TEM figure and (b) SEM figure；
【Fig. 5】For (a) TEM figures of graphene/sulfur compound (GS) and (b) SEM figures；
【Fig. 6】It is graphene in embodiment 1/sulfur compound graphene/sulfur compound (GS) in 0.2C (1C=1675mA
g-1) under charging and discharging curve；
【Fig. 7】For graphene in embodiment 1/sulfur compound graphene/cycle performance of the sulfur compound (GS) under 0.2C；
【Fig. 8】For graphene in embodiment 1/sulfur compound graphene/cycle of the sulfur compound (GS) under 0.5C and 1C
Performance；
【Fig. 9】For cycle performance of the graphene/sulfur compound (GS) under 0.5 and 1C in embodiment 2.
Specific embodiment
Following embodiment is further intended to that present disclosure is further described rather than limits the right of invention
Claimed range.
Embodiment 1
1)g-C3N4Preparation：
Selection melamine is raw material, in air atmosphere, the heating rate of 10 DEG C/min, and 550 DEG C of heat preservation 4h, by product
It is fully ground, you can obtain the g-C of lamella3N4；
2) preparation of graphene oxide：
Graphene oxide is prepared using the Hummers methods of improvement.The concentrated sulfuric acid of 23mL 98% is added in round-bottomed flask,
Under ice bath and stirring condition, 0.5g sodium nitrate is slowly added to, after sodium nitrate is completely dissolved, adds in the expanded graphite powder of 1g；
After 20min, it is slowly added to 3g potassium permanganate in batches, control temperature is below 5 DEG C.After 30min, round-bottomed flask is transferred to oil
In bath, continue to stir 2h under the conditions of 35 DEG C；Temperature is controlled to add in 46mL deionized waters into flask at 98 DEG C, continue to stir
30min；Then the 3%H of 30mL is added in thereto2O2；With 5% hydrochloric acid and deionized water centrifuge washing repeatedly to neutral；Again will
It is placed on dialysis treatment in bag filter；After dialysis treatment, its concentration is measured, is placed in refrigerator and is protected from light refrigeration.
3) preparation of graphene/sulphur composite material (GS)：
Weigh 0.04g g-C3N4With 0.59g sodium thiosulfate ultrasonic disperse in 45mL deionized waters；Measure 20mL GO
Dispersion liquid (2.5mg mL-1) ultrasonic disperse 30min, it is added in above-mentioned dispersion liquid, continues ultrasound 30min；Add in 10mL's
1mol L-1Dilute hydrochloric acid, after abundant mixing, in the pyroreaction kettle for the polytetrafluoroethylene (PTFE) for being transferred to 100mL, 180 DEG C of conditions
Lower hydro-thermal reaction 12h.Reaction is finished after reaction kettle cooling, is obtained a cylindrical black solid, is cleaned with deionized water
Behind surface, it is placed in vacuum drying chamber 60 DEG C of dryings for 24 hours.
5) preparation of electrode film：
Material composition respectively GS, acetylene black, the polytetrafluoroethylene (PTFE) of the cathode film, mass ratio 6:2:2, through overdrying
It is dry, cut out film, tabletting.
6) assembled battery：
Celgard2300 perforated membranes are anode as negative plate, GS electrode films as diaphragm, metal lithium sheet, and addition is electrolysed
Liquid.2025 button cells are assembled into the glove box full of high-purity argon gas.
7) battery performance is tested：
Charge-discharge test, 1.5~2.8V of voltage range are carried out under different multiplying using the progress of blue electrical measurement test system.
As can be seen from Figure 1 graphene/sulfur compound that prepared by embodiment 1 is wherein containing the sulphur member as sublimed sulfur
Element.
The content that sulphur in prepared graphene/sulfur compound can be determined from Fig. 2 thermogravimetric analysis is about 88%；Fig. 4 and
Fig. 5 is substance shape appearance figure, it can be seen that sulphur is well by graphene coated in graphene/sulfur compound.
It is the test to chemical property from the charging and discharging curve of Fig. 6~Fig. 8, illustrates the cyclical stability and again of material
Rate performance.
Embodiment 2
1)g-C3N4Preparation such as embodiment 1；
2) the preparation such as embodiment 1 of graphene/sulphur composite material (GS)；
3) 0.04g g-C are weighed3N4With 0.59g sodium thiosulfate ultrasonic disperse in 45mL deionized waters；The GO of 31mL points
Dispersion liquid (2.5mg mL-1) ultrasonic disperse 30min, it is added in above-mentioned dispersion liquid, continues ultrasound 30min；Add in the 1mol of 10mL
L-1Dilute hydrochloric acid, after abundant mixing, in the pyroreaction kettle for the polytetrafluoroethylene (PTFE) for being transferred to 100mL, hydro-thermal under the conditions of 160 DEG C
React 14h.Reaction is finished after reaction kettle cooling, obtains a cylindrical black solid, after cleaning surface with deionized water,
It is placed in vacuum drying chamber 60 DEG C of dryings for 24 hours.
The content that sulphur in prepared graphene/sulfur compound can be determined from Fig. 3 thermogravimetric analysis is about 71%.
The charging and discharging curve of Fig. 9 is the test to chemical property, illustrates the cyclical stability and high rate performance of material.
Claims (8)
1. a kind of high preparation method for carrying sulphur lithium sulfur battery anode material, it is characterised in that：G-C will be contained3N4, graphene oxide, sulphur
The dispersion liquid of sodium thiosulfate and inorganic acid carry out hydro-thermal reaction to get.
2. a kind of high preparation method for carrying sulphur lithium sulfur battery anode material according to claim 1, it is characterised in that：Oxidation
Graphene and g-C3N4Mass ratio be 10:5~20.
3. a kind of high preparation method for carrying sulphur lithium sulfur battery anode material according to claim 2, it is characterised in that：It is described
g-C3N4It is calcined under protective atmosphere or air atmosphere and 400~600 DEG C of temperature conditions by dicyanodiamine and/or melamine
It obtains.
4. a kind of high preparation method for carrying sulphur lithium sulfur battery anode material according to claim 2, it is characterised in that：It is described
Graphene oxide is made by improved Hummers methods.
5. a kind of high preparation method for carrying sulphur lithium sulfur battery anode material according to claim 1, it is characterised in that：Oxidation
The mass ratio of graphene and elemental sulfur is 8~12:5；Wherein, the quality of elemental sulfur is disproportionated with sodium thiosulfate and inorganic acid
The elemental sulfur quality of generation is reacted to calculate.
6. according to a kind of high preparation method for carrying sulphur lithium sulfur battery anode material of Claims 1 to 5 any one of them, feature
It is：The hydrothermal reaction condition is：At a temperature of 140~200 DEG C, react 8~16 hours.
7. a kind of high load sulphur lithium sulfur battery anode material, it is characterised in that：It is prepared by any one of claim 1~6 method.
8. the high application for carrying sulphur lithium sulfur battery anode material described in claim 7, it is characterised in that：Applied to lithium-sulfur cell.
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| CN109273703A (en) * | 2018-12-10 | 2019-01-25 | 山东大学 | A kind of lithium-sulphur cell positive electrode graphene/sulphur/nickel hydroxide self-supporting composite material and preparation method |
| CN109585807A (en) * | 2018-11-02 | 2019-04-05 | 东莞市迈科新能源有限公司 | Positive electrode and its preparation method and application for lithium-sulfur cell |
| CN109713269A (en) * | 2018-12-26 | 2019-05-03 | 辽宁工程技术大学 | A kind of lithium-sulfur cell polyenoid/S composite positive pole preparation method |
| CN109802107A (en) * | 2018-12-26 | 2019-05-24 | 辽宁工程技术大学 | A kind of preparation method of sodium-ion battery polyene-based composite negative pole material |
| CN109873142A (en) * | 2019-02-22 | 2019-06-11 | 东莞理工学院 | Electrode active material, anode and preparation method thereof and lithium battery |
| CN110783581A (en) * | 2019-08-26 | 2020-02-11 | 浙江工业大学 | Nickel-based MOF/melamine-graphene foam compressible composite material and preparation method and application thereof |
| CN111446451A (en) * | 2020-04-07 | 2020-07-24 | 绍兴诺鼎卫浴洁具股份有限公司 | Co-Ni carbon material loaded g-C3N4-rGO positive electrode material of lithium-sulfur battery and preparation method thereof |
| CN113130880A (en) * | 2021-04-12 | 2021-07-16 | 肇庆市华师大光电产业研究院 | Preparation method of positive electrode sulfur-fixing carrier material of lithium-sulfur battery |
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Cited By (10)
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| CN109585807A (en) * | 2018-11-02 | 2019-04-05 | 东莞市迈科新能源有限公司 | Positive electrode and its preparation method and application for lithium-sulfur cell |
| CN109273703A (en) * | 2018-12-10 | 2019-01-25 | 山东大学 | A kind of lithium-sulphur cell positive electrode graphene/sulphur/nickel hydroxide self-supporting composite material and preparation method |
| CN109713269A (en) * | 2018-12-26 | 2019-05-03 | 辽宁工程技术大学 | A kind of lithium-sulfur cell polyenoid/S composite positive pole preparation method |
| CN109802107A (en) * | 2018-12-26 | 2019-05-24 | 辽宁工程技术大学 | A kind of preparation method of sodium-ion battery polyene-based composite negative pole material |
| CN109713269B (en) * | 2018-12-26 | 2021-05-25 | 辽宁工程技术大学 | Preparation method of polyene/S composite positive electrode material for lithium-sulfur battery |
| CN109802107B (en) * | 2018-12-26 | 2021-11-30 | 辽宁工程技术大学 | Preparation method of polyalkenyl composite negative electrode material for sodium ion battery |
| CN109873142A (en) * | 2019-02-22 | 2019-06-11 | 东莞理工学院 | Electrode active material, anode and preparation method thereof and lithium battery |
| CN110783581A (en) * | 2019-08-26 | 2020-02-11 | 浙江工业大学 | Nickel-based MOF/melamine-graphene foam compressible composite material and preparation method and application thereof |
| CN111446451A (en) * | 2020-04-07 | 2020-07-24 | 绍兴诺鼎卫浴洁具股份有限公司 | Co-Ni carbon material loaded g-C3N4-rGO positive electrode material of lithium-sulfur battery and preparation method thereof |
| CN113130880A (en) * | 2021-04-12 | 2021-07-16 | 肇庆市华师大光电产业研究院 | Preparation method of positive electrode sulfur-fixing carrier material of lithium-sulfur battery |
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